Precursor-driven structural tailoring of iron oxychloride for enhanced heterogeneous Fenton activity

Abstract

Iron oxychloride (FeOCl) is a unique layered material with tunable electronic properties. The conventional synthetic route of chemical vapor transition involves a thermodynamics-driven gas–solid interfacial reaction which often generates macroscopic crystals with stable facets. In this study, through analyzing the effects of the synthetic parameters on the FeOCl synthesis, we discovered the dominant contribution of the α-Fe₂O₃ precursors on the chemical property of the FeOCl product, and subsequently developed a highly-controllable synthetic route of tailoring the FeOCl structures into small sizes and exposed high-energy facets via a facile and scalable mechanical-chemical approach. The synthesized products could be systematically tuned by the ball-milling conditions of the α-Fe₂O₃ precursors. With increased milling time, the FeOCl crystallites demonstrated reduced sizes and more exposed (110) facets. Intriguingly, these small-sized FeOCl catalysts exhibited much faster Fenton-like kinetics than the pristine macroscopic FeOCl materials. Specifically, FeOCl catalysts with a 12-hour milling time showed nearly 39 times higher efficiency toward phenol degradation than the pristine FeOCl. The structure-reactivity relationship was further elucidated using the combinatory analysis via density functional theory calculation, electron paramagnetic resonance and radical quenching probe experiments. This work provides a rationale for tailoring the surface structures of FeOCl crystallites for potential applications in environmental catalysis.

Key words： FeOCl; mechanical activation; heterogeneous Fenton reaction; ball milling

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

This work was partially supported by the National Key Projects for Fundamental Research and Development of China (Grant No. 2019YFC1906700), the National Natural Science Foundation for Outstanding Young Scholars (Grant No. 22222602) and the National Natural Science Foundation of China (Grant No. 21876049).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-023-2330-z and is accessible for authorized users.

References

1 Lind M. Refinement of the crystal structure of iron oxychloride. Acta Crystallographica Section B: Structural Crystallography and Crystal Chemistry, 1970, 26(8): 1058–1062

2 Yang X J, Xu X M, Xu J, Han Y F. Iron oxychloride (FeOCl): an efficient Fenton-like catalyst for producing hydroxyl radicals in degradation of organic contaminants. Journal of the American Chemical Society, 2013, 135(43): 16058–16061

3 Sun M, Zucker I, Davenport D M, Zhou X C, Qu J H, Elimelech M. Reactive, self-cleaning ultrafiltration membrane functionalized with iron oxychloride nanocatalysts. Environmental Science & Technology, 2018, 52(15): 8674–8683

4 Sun M, Chu C H, Geng F L, Lu X L, Qu J H, Crittenden J, Elimelech M, Kim J H. Reinventing Fenton chemistry: iron oxychloride nanosheet for pH-insensitive H₂O₂ activation. Environmental Science & Technology Letters, 2018, 5(3): 186–191

5 Zhou P, Ren W, Nie G, Li X J, Duan X G, Zhang Y L, Wang S B. Fast and long-lasting iron(III) reduction by boron toward green and accelerated Fenton chemistry. Angewandte Chemie International Edition, 2020, 59(38): 16517–16526

6 Xiong Y, Li H C, Liu C W, Zheng L R, Liu C, Wang J O, Liu S J, Han Y H, Gu L, Qian J S, Wang D. Single-atom Fe catalysts for Fenton-like reactions: roles of different N species. Advanced Materials, 2022, 34(17): 2110653

7 Huang X P, Chen Y, Walter E, Zong M R, Wang Y, Zhang X, Qafoku O, Wang Z M, Rosso K M. Facet-specific photocatalytic degradation of organics by heterogeneous Fenton chemistry on hematite nanoparticles. Environmental Science & Technology, 2019, 53(17): 10197–10207

8 Liu M Y, Xu Y, Zhao Y J, Wang Z, Shi D Y. Hydroxyl radical-involved cancer therapy via Fenton reactions. Frontiers of Chemical Science and Engineering, 2022, 16(3): 345–363

9 Zhu Y P, Zhu R L, Xi Y F, Zhu J X, Zhu G Q, He H P. Strategies for enhancing the heterogeneous Fenton catalytic reactivity: a review. Applied Catalysis B: Environmental, 2019, 255: 117739

10 Yang X F, Wang A Q, Qiao B T, Li J, Liu J Y, Zhang T. Single-atom catalysts: a new frontier in heterogeneous catalysis. Accounts of Chemical Research, 2013, 46(8): 1740–1748

11 Pieczko M E, Breen J J. Atomic force microscopy studies of iron oxychloride. Langmuir, 1995, 11(4): 1412–1414

12 Hwang S R, Li W H, Lee K C, Lynn J W, Wu C G. Spiral magnetic structure of Fe in van der Waals gapped FeOCl and polyaniline-intercalated FeOCl. Physical Review B: Condensed Matter, 2000, 62(21): 14157–14163

13 Li S S, Lin Y C, Hong J H, Gao B, Lim H E, Yang X, Liu S, Tateyama Y, Tsukagoshi K, Sakuma Y, Suenaga K, Taniguchi T. Mixed-salt enhanced chemical vapor deposition of two-dimensional transition metal dichalcogenides. Chemistry of Materials, 2021, 33(18): 7301–7308

14 Wang D W, Gilliland S E III, Yi X B, Logan K, Heitger D R, Lucas H R, Wang W N. Iron mesh-based metal organic framework filter for efficient arsenic removal. Environmental Science & Technology, 2018, 52(7): 4275–4284

15 Pham A L T, Lee C, Doyle F M, Sedlak D L. A silica-supported iron oxide catalyst capable of activating hydrogen peroxide at neutral pH values. Environmental Science & Technology, 2009, 43(23): 8930–8935

16 Espinosa J C, Catala C, Navalon S, Ferrer B, Alvaro M, Garcia H. Iron oxide nanoparticles supported on diamond nanoparticles as efficient and stable catalyst for the visible light assisted Fenton reaction. Applied Catalysis B: Environmental, 2018, 226: 242–251

17 Zhu Z X, Chen Y, Gu Y, Wu F, Lu W Y, Xu T F, Chen W X. Catalytic degradation of recalcitrant pollutants by Fenton-like process using polyacrylonitrile-supported iron(II) phthalocyanine nanofibers: intermediates and pathway. Water Research, 2016, 93: 296–305

18 Zou J, Ma J, Chen L W, Li X C, Guan Y H, Xie P C, Pan C. Rapid acceleration of ferrous iron/peroxymonosulfate oxidation of organic pollutants by promoting Fe(III)/Fe(II) cycle with hydroxylamine. Environmental Science & Technology, 2013, 47(20): 11685–11691

19 Yao Y J, Cai Y M, Wu G D, Wei F Y, Li X Y, Chen H, Wang S B. Sulfate radicals induced from peroxymonosulfate by cobalt manganese oxides (Co_xMn_3−xO₄) for Fenton-like reaction in water. Journal of Hazardous Materials, 2015, 296: 128–137

20 Yuan F, Hu C, Hu X X, Wei D B, Chen Y, Qu J H. Photodegradation and toxicity changes of antibiotics in UV and UV/H₂O₂ process. Journal of Hazardous Materials, 2011, 185(2): 1256–1263

21 Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Physical Review B: Condensed Matter, 1996, 54(16): 11169–11186

22 Perdew J P, Zunger A. Self-interaction correction to density-functional approximations for many-electron systems. Physical Review B: Condensed Matter, 1981, 23(10): 5048–5079

23 Klimeš J, Bowler D R, Michaelides A. Chemical accuracy for the van der Waals density functional. Journal of Physics Condensed Matter, 2009, 22(2): 022201

24 Klimeš J, Bowler D R, Michaelides A. Van der Waals density functionals applied to solids. Physical Review B: Condensed Matter and Materials Physics, 2011, 83(19): 195131

25 Monkhorst H J, Pack J D. Special points for Brillouin-zone integrations. Physical Review B: Solid State, 1976, 13(12): 5188–5192

26 Zhang J, Jiao X L, Xia Y G, Liu F F, Pang Y P, Zhao X F, Chen D R. Enhanced catalytic activity in liquid-exfoliated FeOCl nanosheets as a Fenton-like catalyst. Chemistry, 2016, 22(27): 9321–9329

27 Pourghahramani P, Forssberg E. Microstructure characterization of mechanically activated hematite using XRD line broadening. International Journal of Mineral Processing, 2006, 79(2): 106–119

28 Williamson G K, Hall W H. X-ray line broadening from filed aluminium and wolfram. Acta Metallurgica, 1953, 1(1): 22–31

29 Lu L, Li L P, Wang X J, Li G S. Understanding of the finite size effects on lattice vibrations and electronic transitions of nano α-Fe₂O₃. Journal of Physical Chemistry B, 2005, 109(36): 17151–17156

30 Arbain R, Othman M, Palaniandy S. Preparation of iron oxide nanoparticles by mechanical milling. Minerals Engineering, 2011, 24(1): 1–9

31 Zeng Y, Gu P F, Zhao Z J, Zhang B, Lin Z C, Peng Y X, Li W, Zhao W T, Leng Y C, Tan P H, Yang T, Zhang Z, Song Y, Yang J, Ye Y, Tian K, Hou Y. 2D FeOCl: a highly in-plane anisotropic antiferromagnetic semiconductor synthesized via temperature-oscillation chemical vapor transport. Advanced Materials, 2022, 34(14): 2108847

32 Fernandez-Izquierdo L, Spera E L, Durán B, Marotti R E, Dalchiele E A, Del Rio R, Hevia S A. CVD growth of hematite thin films for photoelectrochemical water splitting: effect of precursor-substrate distance on their final properties. Molecules, 2023, 28(4): 1954

33 Tadic M, Trpkov D, Kopanja L, Vojnovic S, Panjan M. Hydrothermal synthesis of hematite (α-Fe₂O₃) nanoparticle forms: synthesis conditions, structure, particle shape analysis, cytotoxicity and magnetic properties. Journal of Alloys and Compounds, 2019, 792: 599–609

34 Zoltán V, Mária K, Magdolna H. Gas-phase structures of iron trihalides: a computational study of all iron trihalides and an electron diffraction study of iron trichloride. Inorganic Chemistry, 2010, 49(3): 1039–1045

35 Wang Q C, Lei Y P, Wang Y C, Liu Y, Song C Y, Zeng J, Song Y H, Duan X D, Wang D S, Li Y D. Atomic-scale engineering of chemical-vapor-deposition-grown 2D transition metal dichalcogenides for electrocatalysis. Energy & Environmental Science, 2020, 13(6): 1593–1616

36 Ji X X, Wang H F, Hu P J. First principles study of Fenton reaction catalyzed by FeOCl: reaction mechanism and location of active site. Rare Metals, 2019, 38(8): 783–792

37 Pajączkowska A, Majcher K. The chemical vapour transport of Mn₃Fe₂Ge₃O₁₂ garnet. Journal of Materials Science Letters, 1986, 5(4): 487–488

38 Ferrenti A M, Siegler M A, Gao S Y, Ng N, McQueen T M. ScSI: a new exfoliatable semiconductor. Chemistry of Materials, 2022, 34(12): 5443–5451

39 Dai Y D, Yu Z, Huang H B, He Y, Shao T, Hsia Y F. Thermal decomposition of iron oxychloride as studied by thermal analysis, X-ray diffraction and Mössbauer spectroscopy. Materials Chemistry and Physics, 2003, 79(1): 94–97

40 Dai C, Tian X K, Nie Y L, Fu W, Wang J T. Effect of the interaction mode of H₂O₂ over CuMnO₂ surface on •OH generation for efficient degradation of ofloxacin: activity and mechanism. Chemical Engineering Journal, 2023, 451: 138749

41 Wang Y, Zhong Z, Chen Y, Ng C T, Lin J. Controllable synthesis of Co₃O₄ from nanosize to microsize with large-scale exposure of active crystal planes and their excellent rate capability in supercapacitors based on the crystal plane effect. Nano Research, 2011, 4(7): 695–704

42 Zhao C, Guo S E, Li Q, Liu J N, Zheng M, Xiao X D, Jiang B J, Fu H G. Supramolecular precursor derived loofah sponge-like Fe₂O_x/C for effective synergistic reaction of Fenton and photocatalysis. Nano Research, 2022, 15(3): 1949–1958

43 Tan X J, Ding W H, Jiang Z Y, Sun L X, Huang Y X. Reinventing MoS₂ co-catalytic Fenton reaction: oxygen-incorporation mediating surface superoxide radical generation. Nano Research, 2022, 15(3): 1973–1982

44 Yamashita T, Hayes P. Analysis of XPS spectra of Fe²⁺ and Fe³⁺ ions in oxide materials. Applied Surface Science, 2008, 254(8): 2441–2449

45 Luo J M, Sun M, Ritt C L, Liu X, Pei Y, Crittenden J C, Elimelech M. Tuning Pb(II) adsorption from aqueous solutions on ultrathin iron oxychloride (FeOCl) nanosheets. Environmental Science & Technology, 2019, 53(4): 2075–2085

46 Mijangos F, Varona F, Villota N. Changes in solution color during phenol oxidation by Fenton reagent. Environmental Science & Technology, 2006, 40(17): 5538–5543

47 Feng Y, Han K, Jiang T, Bian Z F, Liang X, Cao X, Li H, Wang Z L. Self-powered electrochemical system by combining Fenton reaction and active chlorine generation for organic contaminant treatment. Nano Research, 2019, 12(11): 2729–2735

48 Li X Y, Cui Y H, Feng Y J, Xie Z M, Gu J D. Reaction pathways and mechanisms of the electrochemical degradation of phenol on different electrodes. Water Research, 2005, 39(10): 1972–1981